Equilibrated mixtures of organopolysiloxanes containing sulfonic acid groups and process for the preparation of such organopolysiloxanes

Abstract

The disclosed equilibrated mixtures of organopolysiloxanes containing sulfonic acid groups have the average unit formula ##EQU1## In this formula, b has a value of from 0 to 50, preferably 0 to 10; A IS A NUMERAL WHICH IS SELECTED SO THAT THE AVERAGE UNIT MOLECULE COMPRISES 2 TO 100, PREFERABLY 4 TO 50 SILICON ATOMS AND THE RATIO OF R 3 groups which are not linked to trifunctional Si-atoms to R 3 groups which are linked to trifunctional Si-atoms is at least 4; R 3 is alkyl, substituted alkyl, aryl or substituted aryl; and X is halogen, ##EQU2## wherein R 1 is alkyl, aryl or alkaryl, or ##EQU3## wherein R 4 is divalent hydrocarbon, at least 3% of X constituting said ##EQU4## or ##EQU5## groups, the number of said ##EQU6## groups in the unit not exceeding 10. The novel equilibrated mixtures of sulfonic acid groups containing organopolysiloxanes may be directly used as equilibration and polymerization catalysts for organopolysiloxane systems. They also serve as intermediaries in the production of foam stabilizers. Numerous other uses for the novel compounds are disclosed in the application.

What is claimed is: 
     
       1. An equilibrated mixture of organopolysiloxanes of the average unit formula ##EQU33## wherein: b = 0 - 50; a is a numeral which is selected so that the average unit molecule comprises 2 - 100 silicon atoms and the ratio of R.sup. 3 groups which are not linked to trifunctional Si-atoms to R 3  groups which are linked to trifunctional Si-atoms is at least 4;   R 3  is alkyl, substituted alkyl selected from the group consisting of --(CH 2 ) 2  --CN, --CH 2  --Br, --(CH 2 ) 3  Cl, ##SPC5## ##EQU34## and --(CH 2 ) 3  --0--alkyl, vinyl, or aryl and X is halogen, ##EQU35## wherein R 1  is alkyl, aryl or alkaryl, or ##EQU36## wherein R 4  is divalent hydrocarbon, at least 3% of X constituting said ##EQU37## or ##EQU38## groups, the number of said ##EQU39## groups in the unit not exceeding 10, and a portion of X may be trialkylsiloxy and wherein the free valences are saturated by intermolecular or intramolecular linking.   
     
     
       2. The mixture of claim 1, wherein b = 0 -10. 
     
     
       3. The mixture of claim 1, wherein a is selected so that the average unit molecule comprises 4 -50 silicon atoms. 
     
     
       4. The mixture of claim 1, wherein R 3  is methyl. 
     
     
       5. The mixture of claim 1, wherein R 3  is a group which is inert in the presence of acids and is alkyl, substituted alkyl, or aryl. 
     
     
       6. The mixture of claim 5, wherein R 3  is one or more selected from the group consisting of -CH 3 , --C 2  H 5 , n--C 3  H 7  --, --CH=CH 2 , n--C 8  H 17  --, --(CH 2 ) 2  --CN, --CH 2  --Br, --(CH) 2 ) 3  Cl, ##SPC6## ##EQU40## and --(CH 2 ) 3  --0--alkyl. 
     
     
       7. The mixture of claim 1, wherein the R 3  which is linked to the trifunctional Si-atom is at least partially --O-- 0 .5 
     
     
       8. The mixture of claim 1, wherein R 4  is alkylene of 2 - 18 carbon atoms or arylene. 
     
     
       9. The mixture of claim 8, wherein the arylene is phenylene, naphthylene or 4,4'-diphenylenemethane. 
     
     
       10. The mixture of claim 1, wherein said halogen is chlorine. 
     
     
       11. The mixture of claim 1, wherein R 1  is methyl, ethyl, propyl, isopropyl, butyl, isobutyl, phenyl, p-toluolyl or p-dodecylphenyl. 
     
     
       12. The mixture of claim 1, wherein at least 20% of X are ##EQU41## groups. 
     
     
       13. The mixture of claim 1, wherein X is entirely constituted of ##EQU42## groups. 
     
     
       14. The mixture of claim 1, wherein a portion of the X-groups are trialkylsiloxy groups. 
     
     
       15. The mixture of claim 14, wherein the trialkylsiloxy is trimethylsiloxy. 
     
     
       16. An equilibrated mixture of organopolysiloxanes of the average unit formula ##EQU43## wherein: b = 0 - 10; a is a numeral which is selected so that the average unit molecule comprises 4 - 50 silicon atoms and the ratio of R 3  groups which are not linked to trifunctional Si-atoms to R 3  groups which are linked to trifunctional Si-atoms is at least 4;   R 3  is one or more selected from the group consisting of --CH 3 , --C 2  H 5 , n--C 3  H 7  --, --CH=CH 2 , n--C 8  H 17  --, --(CH 2 ) 2  --CN, --CH 2  --Br, --(CH 2 ) 3  Cl, ##SPC7## ##EQU44## and (CH 2 ) 3  --0--alkyl and X is chlorine, ##EQU45## wherein R 1  is alkyl, aryl or aralkyl, or ##EQU46## , wherein R 4  is alkylene of 2 -  18 carbon atoms, phenylene, napththylene or 4,4'-diphenylenemethane, at least 20% of X being said ##EQU47## and the number of ##EQU48## in the average molecule not exceeding 10 and wherein the free valences are saturated by intermolecular or intramolecular linking.   
     
     
       17. A process of preparing equilibrated organopolysiloxane mixtures of claim 1 having organosulfonic acid groups linked to silicon, which comprises reacting organohalogensilanes or mixtures thereof which are convertible into said polysiloxanes with a. an amount of water which is insufficient to split off all halogen groups and   b. organosulfonic acid in amount of 0.005-1 mole/valence silane.   
     
     
       18. A process as claimed in claim 17, wherein the organohalogensilane or the mixtures thereof are first partially hydrolyzed with an amount of H 2  O which is insufficient for splitting off all halogen groups, whereupon the organopolysiloxane thus obtained and which comprises terminal halogen groups is reacted with said organosulfonic acid. 
     
     
       19. A process as claimed in claim 16, wherein said organohalogensilanes are organochlorosilanes. 
     
     
       20. A process as claimed in claim 17, wherein said organosulfonic acid corresponds to the formula ##EQU49## wherein R 1  is alkyl, aryl or alkaryl. 
     
     
       21. A process as claimed in claim 20, wherein R 1  is alkyl of 1 to 4 carbon atoms, phenyl, p-toluoyl or p-dodecylphenyl. 
     
     
       22. A process as claimed in claim 17, wherein said organosulfonic acid is a disulfonic acid which links the polysiloxane blocks with each other. 
     
     
       23. An equilibrated mixture of organopolysiloxanes of the average unit formula ##EQU50## 
     
     
       24. An equilibrated mixture of organopolysiloxanes of the average unit formula ##SPC8## 
     
     
       25. An equilibrated mixture of organopolysiloxanes of the average unit formula ##SPC9##